ANAEROBIC DIGESTION PROCESSES

Functional definition of Anaerobic = absence of oxygen or nitrate.

Role of anaerobic processes in wastewater treatment
1. Enhanced biological phosphate removal (EBPR)
2. Sludge stabilization = reduction in volatile (bioreactive) solids from
primary, biofilm, and waste activated sludge
3. Reduction in pathogens in sludge
4. Energy recovery as biofuels production, primarily methane (CH4)
For 2-4, the unit process is the anaerobic digester.
General characteristics: mixed suspended solids, complex microorganism
communities, long hydraulic and solids residence time (30-60 days), mesophilic
temperature (~35 C)
Dominant Microbial populations:
Bacteria and Archaea
Rate and extent of stabilization and methane production depend strongly on
population interactions.
Three groups of anaerobic microorganisms in digester populations:
Group I: hydrolytic fermentative bacteria
Group II: Syntrophic acetogenic bacteria (SAB)
Group III: Archaea (methanogens)
Populations, substrates, products and reaction stoichiometries are shown in Figure
1 and Table 1, following.

Fig 1. PARTICULATE HYDROLYSIS: HYDROLYTIC FERMENTATIVE

BACTERIA (Xf)

Complex Biodegradable Particulates, XS

Proteins and carbohydrates, SP

Lipids, SP

Long Chain Fatty Acids, SP

Amino acids and simple

sugars, SP

FERMENTATION, Xf AND ACIDOGENESIS: SYNTROPIC ACIDOGENIC

BACTERIA, XSAB
Volatile (Fatty) Acids:
propionate, butyrate, etc.
(R-COOH), SVA

Hydrogen (H2)

Acetic Acid
(CH3COOH) SA

METHANOGENESIS: ARCHAEA, XM

Methane (CH4), SCH

Table 1. MICROBIAL REACTIONS (MOLAR STOICHIOMETRIES)

I. Fermentation reaction examples (glucose substrate, various VA products)
Product
Reaction
G (kJ/mole glucose)
+
Lactate
C6H12O6 2CH3CH(OH)COO + 2H
-198.1
+
Butyrate
C6H12O6 + 2H2O CH32(CH2)COO + 2HCO3 +2H2 + 3H
-254.4
+
Propionate + acetate 1.5C6H12O6 2CH3CH2COO + CH3COO + HCO3 + 3H
-109.9
Genera: Bacteroides, Clostridium, etc.
II. Syntropic acetogenic reaction examples (various VA substrates, acetate, H2 products)
Substrate
Reaction
G (kJ/mole substrate)
+
Lactate
CH3CH(OH)COO + 2H2O CH3COO + HCO3 + 2H2 + H
- 3.96
+
Butyrate
CH32(CH2)COO + 2H2O 2CH3COO + 2H2 + H
+ 48.1
+
Propionate
CH3CH2COO + 3H2O CH3COO + HCO3 + 3H2 + H
+ 76.1
Genus: Acetobacter
III. Methanogenic reaction examples (various substrates, CH4 product)
Substrate
Acetate
Hydrogen
Formate

Reaction
CH3COO + 2H2O CH4 + HCO34H2 + HCO3- + H+ CH4 + 3H2O
4COO- + H2O + H+ CH4 + 3HCO3-

G (kJ/mole substrate)
- 31.0
- 33.9
- 32.6

Genera: Methanococcus, Methanosarcina, Methanospirillum, etc.

3

Group I. Hydrolytic and Fermentative bacteria (Xf)

Reactions:
a. Hydrolysis of particulate COD (XS) primarily by anaerobic bacteria
(not facultative, generally): Bacteroides, Clostridium, Bifidobacteria
to produce amino acids, simple sugars, lipids and fatty acids.
Hydrolysis reactions are not considered to be growth related:
-XS + SP = 0

(COD basis)

Where Xf = population of hydrolytic/fermenting bacteria and SP = soluble

hydrolysis products
-rXS = rSP
!!
!!" = !!

!! +

!!
!!

!!
!!

b. Fermentation of hydrolysis products by same strains of anaerobic

bacteria (reactions are growth linked). Products are volatile fatty acids
(lactate, propionate, butyrate, formate), alcohols, in addition to cells.
- SP + YfXf + YVASVA = 0

(COD basis)

Where Yf = fermenting bacteria cell growth/hydrolyzed products consumed and

YVA = volatile acids produced/hydrolysis products consumed, and SVA = soluble
volatile acids
Rearranging so Xf is reference component:
- SP/Yf + Xf + (YVA/Yf)SVA = 0

(COD basis)

Relative rates from stoichiometry:

!!"#
!!"
= !!" =
1
!!"
!!
!!
4

Reference Monod growth rate expression for fermenting bacteria:

!!" = !!

!!
!
!! + !! !

Fermenting bacteria produce protons (acid). Important factor in keeping digester

environment balanced and stable is that consumption of VAs and available
alkalinity matches proton production by fermenters.

Group II. Syntropic acetogenic bacteria (XSAB).

SAB reduce protons to H2 and produce acetate and formate from fermentation
products, as well as CO2. Note that some of these reactions are not
thermodynamically favored (G > 0). They rely on product consumption
(interspecies hydrogen or acetate transfer) by Group III Archaea to drive the
reaction. SAB produce alkalinity, which is useful for buffering digester pH. Some
SABs are inhibited by product (acetate) accumulation.
- SVA + YSABXSAB + YASA = 0

(COD basis)

Where YSAB = SAB cell growth/volatile acids consumed and YA = acetate

produced/volatile acids consumed, and SA = soluble acetate. Rearranging so
reference component is XSAB:
- SVA/YSAB + XSAB + (YA/YSAB)SA = 0

(COD basis)

Relative rates from stoichiometry:

!!

!!

= !!"# =

!!"#

!!"
1
!!"#

Reference Monod growth rate expression for acetogenic bacteria:

!!"# = !!"#

!!"
!!" + !!"

!!
!! + !!

!!"#

Product (acetate) inhibition switching function (when SA >> KA, SAB << ! SAB)
5

Group III. Archaea (XM).

Methane producing microorganisms. Approximately 2/3 of methane is produced
from acetate and 1/3 from hydrogen.
Acetoclastic methane production (using acetate as substrate) is important because
acid is removed and alkalinity is formed. Bicarbonate also acts as electron
acceptor for both SAB and Archaea. Acetoclastic Archaea strains:
Methanosarcina, Methanothrix.
- SA + YMXM + YCHSCH = 0

(COD basis)

Rearranging so XM is reference component:

- SA/YM + XM + (YCH/YM)SCH = 0

(COD basis)

Where YM = archaea cell growth/acetate consumed, YCH = methane

produced/acetate consumed, and SCH = methane.
Reference Monod growth rate expression for Archaea using acetate:
!!"

!!"

!!" = !!

!!

!!
!! + !!

= !!" =

!!"
1
!!

1
!!
!"#
+1
10!!

!!

Note pH switching function as H+ gets larger than 10-7 (more acidic), pH switching
function gets smaller and growth rate decreases.
Another group, not particularly valued, but always active, are sulfate reducing
bacteria (SRB). SRB respire sulfate anaerobically to produce H2S species using
soluble organic compounds, especially acetate and H2, as electron donors.

ANAEROBIC DIGESTION STOICHIOMETRIC AND KINETIC MATRIX

Components
Acetate,
SA
(mg/L COD)

Process

Hydrolysis
Fermentation
Acetogenesis
Methanogenesis

Particulate
COD, XS
(mg/L COD)

Fermenting
Bacteria, XF
(mg/L COD)

Rates
Volatile
Acids, SVA
(mg/L COD)

-1
1
YA/YSAB
-1/YM

YVA/YF
-1/YSAB

YVA = g-volatile acids (COD) produced/g-particulate COD consumed

YF = g-fermenting biomass (COD) grown/g-hydrolysis products
YA = g-acetate produced/g-volatile acid COD consumed
YSAB = g-SAB cell growth (COD)/g-volatile acids (COD) consumed
YM = g-archaea cell growth (COD)/g-acetate (COD) consumed
YCH = g-methane produced (COD)/g-acetate (COD) consumed

XS / X F
(mg-COD-SP/mg-COD-XF/d)
q H = k H
K XS + X S / X F
! SP $
F = F #
& (mg-COD-XF/mg-COD-SP/d)
" K P + SP %

! SVA $! K A $
SAB = SAB #
&#
& (mg-COD-XSAB/mg-COD-SVA/d)
" KVA + SVA %" K A + SA %

S A
1
(mg-COD-X /mg-COD-S /d)
M

=
M
A

[
H
+
]
K
+
S

A
A
+ 1
log
7
10

Soluble
Substrate, SP
(mg/L COD)

Syntrophic
Acetogenic
Bacteria,
XSAB
(mg/L COD)

Methanogen
Archaea, XM
(mg/L COD)

Methane, SCH
(mg/L COD)

1
-1/YF
1
1

YCH/YA

qH*XF
F*XF
SAB*XSAB
M*XM

Hydrolysis product formation rate

Fermenting bacteria growth rate

Acetogenic bacteria growth rate

Methanogenic archaea growth rate

Summary of microbial process issues:

1. Anaerobic digestion depends on coordination of three trophic groups of
microorganisms.
2. The rate determining step depends on digester conditions: carbon substrates,
temperature, pH, etc. Often, it is hydrolysis.
3. Metabolite inhibition (especially pH, acetate) can determine process
performance. Methanogens need neutral pH.
4. Spatial organization of populations is important, especially SAB and archaea
for interspecies metabolite transfer. Flocculant and mixed suspensions favor
optimal spatial organization.
5. Speculation that significant hydrogen resides in micro-environment rather
than bulk liquid or gas phases and may not be measurable even though it is a
substrate.

Example. Anaerobic digester is CSTR, T = 35 C, Q = 3,000 m3/d, influent is

CODXS = 10,000 g/m3. Overall yield for mixed population, Y = 0.04 g cells
produced/g-COD destroyed, 50% of influent COD is destroyed, 70% of the
digester gas produced is methane (CH4) and 30% is CO2.
Find the rate of methane production in m3/day under steady-state condition.
Steady-state mass balance for COD on digester CSTR:
0 = CODXS,IN COD XS,OUT COD CODCH4,OUT
0 = Q(CODXS,IN) Q(0.5 CODXS,IN) QY(1-0.5)CODXS,IN RCOD-CH4
RCOD-CH4

= Q CODXS,IN (1 0.5 -0.02) = 3,000(10,000)(0.48)

= 1.44 x 107 g-COD-CH4/day

Assume CH4 is ideal gas p = 1 atm, T = 35 C.

! !" 0.082057(273 + 35)
!
=
=
= 25.3
!
!
1 !"#
!"#$

!
!
1 !"#$!"!
!!"!
= 25.3
= 0.4
!
!"#$ 64!!"#!"!
!!"#!"!
RV, COD-CH4 = 1.44 x 107 g CODCH4/day (0.4 LCH4/g CODCH4)10-3 m3/L
= 5,800 m3/day CH4

Total volume of gas produced/d = 5,800/0.7 = 8,200 m3/day digester gas.

GENERAL ANAEROBIC DIGESTER PROCESS CHARACTERISTICS

1. Suspended growth, mixed system (CSTR no recycle. Feed rate is too low
compared with process volume to bother with batch or semi-batch
simulation)
2. Low growth rate and low cell yields for bacteria and archaea, compared with
aerobic heterotrophs.
3. Heated: 35 C for mesophilic, 55 C for thermophilic
4. Reducing environment: ORP = -200 to -400 mV
5. Floating cover for gas separation and storage
6. Mixing and heating operation often use same equipment
Typical design parameters for typical mesophilic high rate digester:
15 d < = < 20 d
Process Control:
1. Consistency in sludge feed (primary and secondary fractions) and feed rate.
Spikes in COD loading can produce excess acid due to rapid growth of
fermenting bacteria.
2. Alkalinity, typically 2 to 5 g-CaCO3/L. Source is biological reactions, but
can be added if pH drops too low.
Typical high rate mesophilic digester performance
1. Typical TS reduction range = 45 50%
2. Typical VS reduction range = 55 65%
3. Biogas production 0.5 m3/kg-COD consumed
4. Methane production 0.35 m3/kg-COD consumed

10

BioWin Anaerobic Digester Example

Steady state solution
SRT: 20 days
Temperature: 35.0
Flowsheet

Configuration information for all Anaerobic Digester units

Physical data
Element name
Anaerobic
Digester0

Volume
[m3]
60000

Area [m2]
10000.

Depth
[m]
6.0

Head space
volume
20000.

Operating data Average (flow/time weighted as required)

Element name
Pressure pH
Anaerobic
103.0
7.0
Digester0
Element name
Anaerobic
Digester0

Average
Temperature
35.0

Configuration information for all COD Influent units

Element
name

Flow
3
(m /d)

COD
mg/L

TKN
mg
N/L

Total
P
mgP/L

pH

Alk
mM

COD in

3000

10000

600.

50.

7.30

10

Inorg
S.S.
mgTS
S/L
2000.

Ca
mg/L

Mg
mg/L

DO
mg/L

160

25.

0.

11

Anaerobic Digester Effluent,

BioWin Simulation
Water Quality Components

Conc.
(mg/L)

Mass rate
(kg/d)

Volatile suspended solids

Total suspended solids
Particulate COD
Filtered COD
Total COD
Soluble PO4-P
Total P
Filtered TKN
Particulate TKN
Total Kjeldahl Nitrogen
Filtered Carbonaceous BOD
Total Carbonaceous BOD
Nitrite + Nitrate
Total N
Total inorganic N
Alkalinity
pH
Volatile fatty acids
Total precipitated solids
Total inorganic suspended
solids
Ammonia N
Nitrate N

2237.18
4253.85
3544.99
1172.99
4717.98
17.56
50.00
478.94
113.88
592.82
122.13
899.51
0.00
592.82
476.72
16.28
6.49
134.95
0
2016.67

6711.53
12761.54
10634.98
3518.96
14153.94
52.68
150.00
1436.82
341.65
1778.47
366.39
2698.52
0.00
1778.47
1430.17
48.83

476.72
0.00

1430.17
0.00

Operation and Performance

Hydraulic residence time
Flow
Gas flow rate (dry)
Methane content
Carbon dioxide content
Hydrogen content
Ammonia content
VSS destruction

Value
480.00
3000.00
8368.77
72.63
26.31
0.09
0.46
44.96

Units
hours
m3/d
m3/d
%
%
%
%
%

Notes

All NH4-N

mmol/L, kmol/d
A bit low

404.85
0.00
6050.01

Compare with
Pg 9 example
8,200 m3/d
70%
30%

50%

12